Sensitive Detection of Nuclear Quadrupole Interactions in Solids

Abstract

The pure nuclear quadrupole resonance of a low-abundance spin species in zero field is observed for molar concentrations as low as one part in ${10}^{7}$ by the application of a nuclear-double-resonance method. The quadrupole resonance is measured in terms of a decrease in the magnetic order of abundant nuclei which are dipolar-coupled to the low-abundance nuclear species. The double-resonance process is analyzed from the point of view of two energy reservoirs coupled by a dipolar perturbation, and spin diffusion among abundant nuclei is included phenomenologically. Radio-frequency power, which causes the main quadrupole transitions of rare spins, is frequency-modulated to provide saturation in the rotating frame and to enable identification of unknown spin transitions. The pure nuclear quadrupole resonance of Na and Cl nuclei near impurities and imperfections in NaCl is measured. Particular attention is given to the resonances associated with ${\mathrm{K}}^{+}$ and ${\mathrm{Br}}^{\ensuremath{-}}$ ions injected as impurities into the NaCl lattice. An unsuccessful search in zero field has been made for the naturally abundant 0.0156% deuterium quadrupole resonance in CaS${\mathrm{O}}_{4}$\ifmmode\cdot\else\textperiodcentered\fi{}2${\mathrm{H}}_{2}$O and ${\mathrm{C}}_{10}$${\mathrm{H}}_{8}$, where the proton resonance is monitored as the abundant nuclear species. The proton dipolar absorption in zero magnetic field is anomalously broad and overlaps too much with the deuterium quadrupole resonance to permit independent observation of the latter. A narrowing of proton dipolar absorption in zero field is observed for strong radio-frequency fields larger than internal dipole fields.